Continuous enzymatic synthesis of Z-kyotorphin amide in an enzyme-immobilized fixed-bed reactor

α-Chymotrypsin immobilized on natural and inexpensive supports such as diatomaceous earth was used as catalyst for Z-Tyr-Arg-NH₂ (Z-kyotorphin amide) synthesis. In order to obtain the optimal reaction conditions, a 2² factorial experimental design was used. The factors considered were cosolvent (dimethylformamide) concentration and temperature; optimal product yield was achieved at 40% (v/v) dimethylformamide and 25°C. A sequential kinetic model was considered which generally gave good agreement between experimental and theoretical data for continuous synthesis of Z-kyotorphin amide in a packed-bed immobilized reactor system. The activation energy for the synthesis was determined to be 48.0 ± 2.3 kJ mol^?1.     

Phosphatase active cross-flow microfiltration poly(vinylidene difluoride) bioreactor

Alkaline phosphatase from human placenta has been chemically immobilized on a hydrophilic cross-flow microfiltration membrane made from poly(vinylidene difluoride) (PVDF) derivatized with 1,1′-carbonyldiimidazole. The physicochemical characterization of the immobilized biocatalyst paid special attention to the irreversibility of the bonding of the enzyme to the support, the effects of pH, temperature and ionic strength on this activity, the existence of limitations of internal and external diffusion for H⁺, substrate and/or products, and the kinetic behavior (intrinsic and/or effective) of the immobilized enzyme. With respect to enzyme stability, patterns of hysteresis or memory are proposed, to account for a catalytic activity affected by previous experimental events and situations. The intrinsic kinetic behaviour, rate versus substrate concentration in the absence of diffusional restrictions, was analysed graphically and numerically (by non-linear regression and by utilizing the F statistical test for model discrimination), postulating a minimum rational rate equation of 2:2 degree in substrate concentration. In concordance, a mechanistic kinetic scheme for the catalytic enzyme action has been postulated.     

Catalyst effectiveness in low-temperature water—gas shift reaction

A procedure has been developed for a priori prediction of intraparticle diffusion effects in low temperature water—gas shift reaction. Use is made of transport characteristics of the Cu/ZnO/A1₂O₃ pelleted catalyst determined independently by combination of diffusion and permeation results obtained under nonreactive conditions. The porous medium is described by the mean transport pore model and diffusional behaviour of the multicomponent reaction mixture by a modified Stefan-Maxwell equation. Using data from kinetic region obtained at 200°C, it was possible to predict the performance of a bench-scale reactor packed with pelleted catalyst at 200°C and 220°C satisfactorily.     

The effect of electrolyte flow rate and temperature on corrosion and protection of Al–2.5 Mg alloy by (+)-catechin

The effects of flow rate and temperature on the corrosion behaviour of the Al–2.5 Mg alloy in a 3% NaCl solution and the inhibiting efficiency of (+)-catechin on the corrosion of the same alloy have been examined. Measurements were carried out in a flow-through cell, at different flow rates (v ₁ = 0.0029 m s⁻¹, v ₂ = 0.0059 m s⁻¹ and v ₃ = 0.0118 m s⁻¹) and temperatures (20, 30, 40 °C). Electrochemical parameters for the Al–2.5 Mg alloy were determined by polarisation techniques and electrochemical impedance spectroscopy (EIS). Increased flow rate and temperature cause a stronger corrosion attack on the alloy. The addition of (+)-catechin inhibited corrosion at all temperatures and flow rates. The inhibitor efficiency decreased with increase in flow rate and temperature.     

Kinetics of polyesterification of 1,3-(dicarboxymethoxy) benzene with tetraethylene glycol

The polyesterification of 1,3-(dicarboxymethoxy)benzene with tetraethylene glycol in both equimolar and nonequimolar ratios were studied over the range of 120–160°C in the absence and presence of p-toluenesulphonic acid as catalyst. The experimental results for uncatalyzed reactions agreed quite well with the kinetic equation proposed by Flory. The kinetic equations for acid-catalyzed reactions, however, are in agreement with the kinetic equation proposed by Lin and Hsieh. The kinetic equations were ?d[COOH]/dt = k₁[COOH]²[OH] and ?d[COOH]/dt = k₂[COOH]² for uncatalyzed and acid-catalyzed polyesterfications, respectively. The rate constants for uncatalyzed and acid-catalyzed reactions were calculated by using the method of least squares for various values of initial molar ratio between [OH] and [COOH]. Also, the activation energies were calculated.     

Studies on polycrystalline layered ceramic oxide: LiFeVO4

Abstract

A new polycrystalline layered ceramic oxide, LiFeVO₄, has been prepared by a standard solid state reaction technique. The preparation conditions were optimised using thermogravimmetric analysis (TGA) technique. Material formation under the reported conditions was confirmed by X-ray diffraction studies. A preliminary structural analysis indicated that the crystal structure was orthorhombic with lattice parameters: a=4·3368 Å, b=13·1119 Å and c=16·3426 Å. The phase morphology and surface property were studied by scanning electron microscopy. Complex impedance analysis of the sample indicated bulk contribution to electrical properties at T≤125°C, grain boundary effects at the temperatures ≥125°C, negative temperature coefficient of resistance (NTCR) effect and evidence of temperature dependent electrical relaxation phenomena in the sample. The dc conductivity σ_dc shows typical Arrhenius behaviour when observed as a function of temperature. The activation energy value was estimated to be 0·24 eV. The value of σ_dc, evaluated from complex impedance spectrum, shows a jump of nearly two orders of magnitude at higher temperature (～1·24 × 10^?5 S cm^?1 at 350°C) when compared with that of σ_dc (1·14 × 10^?6 S cm^?1 at 50°C). Alternating current conductivity spectrum obeys Jonscher's universal power law. The results of σ_ac v. temperature are also discussed.     

Mathematical Modeling of Mass Transfer during Convective Dehydration of Brown Algae Macrocystis Pyrifera

The aim of this research was to study and to model the drying kinetics of the brown algae Macrocystis pyrifera at 50, 60, 70, and 80°C. GAB equation showed a good fit on the sorption experimental data. Fick's diffusional model, together with Newton, Henderson-Pabis, Page, modified Page, logarithmic, and Midilli-Kukuc models were applied on the drying kinetics of the alga. The D_we increased from 5.56 to 10.22 × 10^?9 m²/s as temperature increased from 50 to 80°C. Midilli-Kukuc and logarithmic models obtained the best-fit quality for drying curves based on the statistical tests. In consequence, both models are excellent tools for estimating the drying time of this product.     

Urease immobilization on an ion‐exchange textile for urea hydrolysis

Ion‐exchange textiles are used as organic supports for urease immobilization with the aim of developing reactive fibrous materials able to promote urea removal. A non‐woven, polypropylene‐based cation‐exchange textile was prepared using UV‐induced graft polymerization. Urease was covalently immobilized onto the cation‐exchange textile using three different coupling agents: N‐(3‐dimethylaminopropyl)‐N′‐ethylcarbodiimide hydrochloride (EDC), N‐cyclohexyl‐N′‐(b‐[N‐methylmorpholino]ethyl)carbodiimide p‐toluenesulfonate (CMC), and glutaraldehyde (GA). The immobilized biocatalyst was characterized by means of FT‐IR spectrometry, SEM micrographs, dependence of the enzyme activity on pH and temperature, and according to the kinetic constants of the free and immobilized ureases. The biotextile prepared with EDC in the presence of N‐hydroxysuccinimide performs best. The optimum pH was 7.2 for the free urease and 7.6 for the immobilized ureases. The reactivity was maximal at 45 °C for free urease, 50 °C for biotextiles prepared using EDC or CMC, and 55 °C for biotextiles prepared with GA. The activation energy for the immobilized ureases was 4.73–5.67 kcal mol^?1, which is somewhat higher than 4.3 kcal mol^?1 for free urease. The urea conversion for a continuous‐flow immobilized urease reactor is nearly as good as a continuously stirred tank reactor having a much longer residence time, suggesting that the packed bed reactor had sufficient diffusive mixing and residence time to reach nearly optimal results. Urease immobilized on a biotextile using EDC has good storage and operational stability. Copyright © 2006 Society of Chemical Industry     

The specific volume of poly(4-methylpentene-1) as a function of temperature (30°–320°C) and pressure (0–2000 kg/cm2)

The dependence of the specific volume of a commercial sample of poly(4-methylpentene-1) (Mitsui TPX, RT-20, abbr. PMP) on temperature (30°–320°C) and pressure (0–2000 kg/cm²) has been determined. Results are reported in tabular form and as approximate fits, making use of the Tait equation. The data show that the crystalline melting transition of this type of PMP is completed at 235°C under zero pressure and gives indication of a glass transition temperature T_g at about 20°C at p = 0. Its approximate pressure dependence is given by dT_g/dp ≈ 0.015°C kg^?1 cm². The zero pressure results on the melting and glass transitions are in agreement with DTA results. The p-v-T data, quenching experiments, and a determination of the crystalline unit cell (tetragonal, a = b = 18.70 Å, c = 13.54 Å) confirm earlier work indicating that the room-temperature crystalline specific volume of PMP is greater than the amorphous specific volume. This unusual density behavior persists to a temperature of 50–60°C at p = 0 and to temperatures as high as 230–240°C under a pressure of 2000 kg/cm².     

THE DEHYDRATION OF GARLIC. 1.DESORPTION ISOTHERMS AND MODELLING OF DRYING KINETICS

Abstract

Desorption isotherms for 1 mm thick garlic slices were determined at between 25 and 50°C and satisfactorily fitted with the G.A.B. equation. The kinetics of drying of slices of thickness 1.5 - 5.0 mm were determined at between 40 and 60°C using an air flow rate of 2.5 m-s^?, and the conditions affording a high-quality product m the shortest time were identified. After establishing how the effective diffusion coefficient of the garlic slices varied with their moisture content during drying, a diffusional model accounting for these variations was developed and satisfactorily fitted to the experimental kinetic data.     

Kinetics of ylide-initiated radical copolymerization of 4-vinylpyridine and methyl methacrylate

The ylide-initiated radical copolymerization of 4-vinylpyridine (4-VP) with methyl methacrylate (MMA) at 60°C using carbon tetrachloride as inert solvent yields non-alternating copolymers. The kinetic parameters, average rate of polymerization (R_p) and orders of reaction with respect to monomers and initiator, have been evaluated and the kinetic equation is found to be R_pα[ylide]^0.94 [MMA]^1.0 [4-VP]^1.5. The values of the energy of activation and k_p²/k_t are 48 kJ mol^?1 and 6.6 × 10^?5 litre mol^?1s^?1, respectively. The copolymers have been characterized by IR and NMR spectroscopy.     

Effect of imidazolium ionic liquid type on the properties of nitrile rubber composites

We investigated the influence of hydrophilic and hydrophobic imidazolium ionic liquids on the curing kinetic, mechanical, morphological and ionic conductivity properties of nitrile rubber composites. Two room temperature ionic liquids with a common cation—1‐ethyl‐3‐methylimidazolium thiocyanate (EMIM SCN; hydrophilic) and 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM TFSI; hydrophobic)—were used. Magnesium–aluminium layered double hydroxide (MgAl‐LDH; also known as hydrotalcite) was added to carboxylated acrylonitrile–butadiene rubber (XNBR) whereas fumed silica Aerosil 380 was used in acrylonitrile–butadiene rubber (NBR) as reinforcing fillers. NBR compounds were vulcanized with a conventional sulfur‐based crosslinking system whereas XNBR compounds were cured with MgAl‐LDH. The optimum cure time reduction and tensile properties improvement were obtained when both ionic liquids were added at 5 parts per hundred rubber (phr). The results revealed that EMIM SCN and EMIM TFSI induced an increase in the AC conductivity of nitrile rubber composites from 10^?10 to 10^?8 and to 10^?7 S cm^?1, respectively (at 15 phr ionic liquid concentration). The presence of ionic liquids in NBR slightly affected the glass transition temperature (T_g) whereas the presence of EMIM TFSI in XNBR contributed to a shift in T_g towards lower temperatures from ?23 to ?31 °C, at 15 phr loading, which can be attributed to the plasticizing behaviour of EMIM TFSI in the XNBR/MgAl‐LDH system. Dynamic mechanical analysis was also carried out and the related parameters, such as the mechanical loss factor and storage modulus, were determined. © 2013 Society of Chemical Industry     

Rate of imidization of polymerizable reaction mixtures: PMR-15

Imidization of PMR-15 was investigated using Fourier transform infrared spectroscopy (FTIR) as a function of time and temperature. Imidization was performed at 65 ≤ T ≤ 300°C for 3 ≤ t ≤ 150 min. FTIR spectroscopy showed that imidization (measured by the changes in the imide carbonyl absorption at 1778 cm⁻¹) increased with temperature and time. Imidization was found to be nearly completed in 2.5 h at 300°C. Imidization of PMR-15 occurred in three stages: (i) the initial imidization region characterized by gradual reaction followed by (ii) a very rapid reaction region that spans about 0.5 h and (iii) a final imidization region characterized by a gradual reaction and spans about 2 h. An Avrami-type kinetic analysis was used to obtain the reaction order of 1.5 and 1.7 and the rate constant for imidization of 1.3 × 10⁻³ and 1.5 × 10⁻³ min^−3/2; at 135 and 165°C, respectively. Comparison with other kinetic models shows agreement at low conversions (p ≤ 15%). At high conversions of p > 20%, a second-order kinetic model seems to fit the data reasonably well in agreement with the observed order. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2529–2538, 1997     

Viscosity–temperature relationships for cellulose acetate–acetone solutions

Viscosity measurements were made for dilute solutions of three grades of cellulose acetate (acetyl content 39.8%, molecular weight M?_v 30270 to 46250) in acetone in the temperature t range of 10° to 35°C. The data satisfied the Mark-Houwink equation, [η] = KM?, where [η] = limiting viscosity number and K and α are Mark-Houwink constants. The values of [η] and α decreased with increase in temperature, and straight-line correlations were obtained for ?d[η]/dt versus M?_v and log η versus 1/T (absolute temperature). The results are discussed in terms of solution properties of cellulose acetate in acetone and their possible relevance to reverse osmosis membrane science.     

Effect of the Secondary Transition on the Behaviour of Epoxy Adhesive Joints at High Rates of Loading

The shear yield behaviour of a modified epoxy joint has been investigated over a wide range of strain rates (γ˙ = 10^–2 s^–1 – 10⁴s^–1) and at different temperatures (–30°C, 24°C, 60°C, 80°C).

Assuming that high polymers exhibit pure viscous yield, the sharp increase of the yield stress in the strain rate sensitivity at high strain rates is explained in terms of a difference in relaxation times at low strain rates and high strain rates (α and β). The Bauwens's approach, which is a modification of the Ree-Eyring theory, gives an acceptable fit to the data. The yield behaviour of the modified epoxy joint, above a critical strain rate γ˙_β(T), may be described by the sum of the partial stresses τ_α and τ_β required to free the different kinds of molecular motions implied in the deformation process.

A good correlation between high impact resistance and the presence of the β mechanical loss peak in the range of the explored strain rates is established.

At very low temperature (-30°C), the data do not accurately fit the Ree-Eyring equation, meaning a heterogeneous deformation process characterized by the formation of local adiabatic shear bands and a permanent evolution of the molecular structure.     

Methacrylic acid and dodecyl methacrylate (MAc‐DMA) hydrogel for enhanced catalytic activity of lipase of Bacillus coagulans MTCC‐6375

An alkaline thermotolerant bacterial lipase of Bacillus coagulans MTCC‐6375 was purified and immobilized on a methacrylic acid and dodecyl methacrylate (MAc‐DMA) hydrogel. The lipase was optimally bound to the matrix after 20 min of incubation at 55°C and pH 9 under shaking conditions. The matrix‐bound lipase retained approximately 50% of its initial activity at 70–80°C after 3 h of incubation. The immobilized lipase was highly active on medium chain length p‐nitrophenyl acyl ester (C: 8, p‐nitrophenyl caprylate) than other p‐nitrophenyl acyl esters. The presence of Fe³⁺, NH₄⁺, K⁺, and Zn²⁺ ions at 1 mM concentration in the reaction mixture resulted in a profound increase in the activity of immobilized lipase. Most of the detergents partially reduced the activity of the immobilized lipase. The immobilized lipase performed ～62% conversion in 12 h at temperature 55°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1420–1426, 2006     

Dynamic analysis of a fluidized bed reactor for sucrose inversion catalyzed by immobilized invertase

Axial mixing characteristics and performance of a liquid fluidized bed reactor for the sucrose inversion reaction, which was catalyzed by immobilized invertase was studied. The invertase enzyme was immobilized in polyacrylamide gel by the bead polymerization technique. Well-defined spherical gel particles of five different sizes (0.29–3.16 mm) were prepared. Efficiency of the immobilization technique, the optimum working conditions and the kinetic parameters were determined in a batch system. It is shown that as the particle size increases the rate of inversion first increases due to decrease of enzyme loss by leaching and then decreases because of diffusional limitations after a maixmum is reached. The performance of the fluidized bed reactor was investigated dynamically by introducing a step input of substrate at the inlet and analyzing the response curves. These experiments were performed at the optimum temperature (55°C) and using the optimum particle size (2.15 mm). The axial dispersion coefficient was found to increase from 0.45 to 1.26 cm²/s by changing the liquid velocity from 0.32 to 0.58 cm/s.     

Kinetics and modeling of the diffusion‐controlled diallyl terephthalate polymerization

Free radical polymerization kinetics of diallyl terephthalate in bulk was investigated in a wide temperature range from 50°C to 150°C with four different peroxide initiators. Conversion points were measured using Fourier Transform Infrared (FTIR) measurements. The initiator efficiencies and the initiator decomposition rate constants were evaluated from special experiments, applying the theory of dead end polymerization. In addition, the ratios between the degradative and the effective kinetic rate constants to propagation rate constants were obtained from molecular weight measurements at various initiator concentrations. The ratio of chemically controlled termination and propagation rate constant k/k_tc of the polymerization system was obtained using the initial rates of polymerization and the number average molecular weight data between 0.25 · 10^?3 and 15.7 · 10^?3 L mol^?1 s^?1. The glass transition temperature of the polymer, 191°C, was measured by the Alternating Differential Scanning Calorimetry (ADSC) technique. Computed conversions from the developed kinetic model were in good agreement with the conversion and molecular weight measured data. The values of diffusion controlled propagation and termination rate constants k_td0 and k_pd0 with clear and physical meaning were the only two parameters obtained from the developed kinetic model fitting. Polym. Eng. Sci. 44:2005–2018, 2004. © 2004 Society of Plastics Engineers.     

Core-shell structured HZSM-5@mesoSiO2 catalysts with tunable shell thickness for efficient n-butane catalytic cracking

A series of core-shell HZSM-5@mesoSiO₂ with tunable shell thickness from 10 to 70 nm was prepared and studied for n-butane catalytic cracking. With introducing of SiO₂ shell, the catalytic performance of HZSM-5@mesoSiO₂ was largely enhanced, and n-butane conversion rate per Al site reached to 2.43 min⁻¹ over HZSM-5@mesoSiO₂(1:4) at 675°C which is nearly twice to that of HZSM-5 (1.34 min⁻¹). The diffusion property of n-butane over as-prepared sample was quantified by measuring the diffusional time constants using zero length column chromatography technique (ZLC). Combining with chemical reaction kinetic analysis, the quantitative relationship between diffusion property and catalytic performance was effectively established for the first time in n-butane catalytic cracking. Positive linear correlation between diffusional time constant (D/R²) and n-butane conversion rate per Al site could be found, which confirms that diffusion enhancement by hierarchical structure is an effective strategy to improve the activity of HZSM-5 in catalytic cracking.     

Liver alcohol dehydrogenase immobilized on polyvinylidene difluoride

A physical method for immobilization of liver alcohol dehydrogenase (ADH) by hydrophobic adsorption onto a supporting membrane of polyvinylidene difluoride (PVDF) was performed. Simultaneously, a physicochemical characterization of the immobilized enzyme regarding its kinetic behaviour was performed. The activity/pH profile observed points to an effect of pH on activity that is completely different from the case of ADH in solution. The disturbance in the typical bell-shaped profile owing to the fact that the enzyme was immobilized is explained on the basis of a potent limitation to the diffusion of the protons in the support. The findings of the present work also reveal the existence of an effect that limits free external diffusion of the substrate towards and/or the product from the support; this effect seems to be the determinant of the overall rate of the enzymatic reaction and is thus of great importance in the effective kinetic behaviour (v([S])) of immobilized ADH, whose kinetic behaviour is complex (non-Michaelian), as may be seen from the lack of linearity observed in the corresponding double reciprocal and Eadie-Hofstee plots. By non-linear regression numerical analysis of the v([S]) data and application of the F-test for model discrimination, the minimum rate equation necessary to describe the intrinsic kinetic behaviour ofPVDF-immobilized ADH proved to be one of the polynomial quotient type of degree 2:2 (in substrate concentration).